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WO2021164702A1 - Électrode à polarité pouvant être inversée et son utilisation - Google Patents

Électrode à polarité pouvant être inversée et son utilisation Download PDF

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WO2021164702A1
WO2021164702A1 PCT/CN2021/076713 CN2021076713W WO2021164702A1 WO 2021164702 A1 WO2021164702 A1 WO 2021164702A1 CN 2021076713 W CN2021076713 W CN 2021076713W WO 2021164702 A1 WO2021164702 A1 WO 2021164702A1
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intermediate layer
electrode
metal
iridium
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Qite ZHAO
Hongyuan Chen
Junwei XUE
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Magneto Special Anodes Suzhou Co Ltd
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Magneto Special Anodes Suzhou Co Ltd
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Priority to EP21714294.2A priority Critical patent/EP4107310A1/fr
Priority to KR1020227031268A priority patent/KR20220142468A/ko
Priority to US17/800,530 priority patent/US20230107452A1/en
Priority to CA3168177A priority patent/CA3168177A1/fr
Priority to JP2022549337A priority patent/JP2023514281A/ja
Publication of WO2021164702A1 publication Critical patent/WO2021164702A1/fr
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    • Y02E60/30—Hydrogen technology
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Definitions

  • the application relates to, but is not limited to, the field of electrochemistry, in particular to, but is not limited to, an electrode having polarity capable of being reversed and use thereof.
  • An oxygen-evolution titanium electrode as an environment-friendly insoluble anode, has been widely used in electrochemical industry, mainly focusing on fine finishing processes such as electrochemical water treatment, metal element extraction, and electroplating.
  • the oxygen-evolution titanium electrode is mainly composed of pure metal titanium or titanium alloy substrate and noble metal oxide catalyst layer on its surface.
  • the substrate provides conductive and mechanical support.
  • the catalyst layer can greatly reduce the oxygen-evolution potential in aqueous solution through its own redox process to achieve the effect of energy saving.
  • the anode has a long service life depending on its extremely low electrochemical consumption rate.
  • the oxygen-evolution catalyst is mainly iridium oxide, which can be mixed with an oxide of valve-type metal such as titanium, tantalum or niobium to make the coating denser to protect the substrate from passivation too quickly.
  • an alloy or a mixed oxide of valve-type metals such as titanium or tantalum or alloy is also used as an intermediate layer to be interposed between the catalyst layer and the substrate to protect the substrate.
  • the anode surface is in an acidic environment due to the oxygen-evolution reaction and the cathode surface is an alkaline environment due to the hydrogen-evolution reaction. Sediments produced in the acidic environment are generally easy to be removed under alkaline conditions, and vice versa.
  • chlorine-evolution electrodes partially oxygen evolution
  • deposits on the surface of the electrode can be removed by reversing the polarity of the electrodes.
  • oxygen-evolution electrodes the current products cannot reach the acceptable life level after the reversal.
  • Ti can be oxidized at a relatively high rate, forming Ti (III) ions in solution, and in the passive region, Ti is covered by the oxide film and can be oxidized only very slowly.
  • the active state should be avoided and it is better that the anode works in the passive state. Alloying could be used to generate passivity on Ti and it can work in two ways: by inhibiting the anodic half-reaction, or by enhancing the cathodic half-reaction. Alloying elements that have been suggested to induce passivity of Ti by cathodic modification include Pt, Pd, Ni, Mo, etc. In the work of M.
  • the noble metal oxide coating is relatively stable whether being anode or being cathode. But due to the thermal decomposition process, there exists a lot of crack, or more generally defects.
  • the low pH produced by the anode reaction greatly accelerate the corrosion of the substrate and as a common solution, a Ta oxide type interlayer is used, and greatly increase the service lifetime. But inventors founded that this type of interlayer can not solve the lifetime problem of polarity reversal.
  • the electrode In addition, some applications also require the electrode to have the function of reversing the polarity of the electrode, such as electrodialysis membrane stack. In order to maintain the performance of the membrane stack, the polarity of the electrode needs to be periodically reversed. However, the use of chlorine-evolution electrode and sodium chloride polar solution will lead to the pollution problem of relatively large chlorine.
  • the application provides an electrode having polarity capable of being reversed including a substrate, an intermediate layer, and a catalytic layer, the substrate may include a metal or an alloy thereof; the intermediate layer is arranged on the substrate and may include a platinum group metal and a platinum group metal oxide; the catalytic layer is arranged on the intermediate layer and may include a mixed metal oxide.
  • the intermediate layer may include a mixture of metal platinum and iridium dioxide.
  • the sum of the content of platinum and iridium may be 1 g/m 2 -30 g/m 2 , for example, 2 g/m 2 , 3 g/m 2 , 4 g/m 2 , 5 g/m 2 , 7.5 g/m 2 , 8 g/m 2 , 10 g/m 2 , 12 g/m 2 , 15 g/m 2 , 18 g/m 2 , 22 g/m 2 , 25 g/m 2 , 28 g/m 2 etc., based on the metal content.
  • the platinum content (based on the metal content) may be 10 wt%-90 wt%, for example, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, etc., based on the total metal content of the intermediate layer.
  • the iridium content may be 10 wt%-90 wt%, for example, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, etc., based on the total metal content of the intermediate layer.
  • the platinum content (based on the metal content) may be 40 wt%-90 wt%, for example, 50 wt%, 60 wt%, 70 wt%, 80 wt%, etc., based on the total metal content of the intermediate layer; and the iridium content may be 10 wt%-60 wt%, for example, 20 wt%, 30 wt%, 40 wt%, 50 wt%, etc., based on the total metal content of the intermediate layer.
  • the intermediate layer may also contain a metal oxide of any one or more of ruthenium, palladium, and rhodium.
  • the content of metal ruthenium, palladium, rhodium (based on the metal content) of the intermediate layer may be each less than 10 wt%, for example, 1 wt%, 2 wt%, 5 wt%, 8 wt%, etc., based on the total metal content of the intermediate layer.
  • the platinum group metal of the intermediate layer may diffuse into the substrate to form a mixed transition layer. Diffusion can be performed by means of heat treatment, such as sintering.
  • the catalytic layer may include a metal oxide of iridium, and may also include a mixed metal oxide of tantalum and iridium, and may also include tantalum pentoxide and iridium dioxide.
  • the iridium content of the catalytic layer may be 3 g/m 2 -100 g/m 2 , for example, 5 g/m 2 , 8 g/m 2 , 10 g/m 2 , 15 g/m 2 , 20 g/m 2 , 22 g/m 2 , 25 g/m 2 , 30 g/m 2 , 35 g/m 2 , 40 g/m 2 , 50 g/m 2 , 60 g/m 2 , 70 g/m 2 , 80 g/m 2 , 90 g/m 2 , based on the metal content.
  • the iridium content (based on the metal content) may be 20 wt%-90 wt%, for example, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, etc., based on the total metal content of the catalytic layer.
  • the tantalum content (based on the metal content) may be 10 wt%-80 wt%, for example, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, etc., based on the total metal content of the catalytic layer.
  • the catalytic layer may further contain a metal oxide of any one or more of ruthenium, palladium, rhodium, titanium, niobium, zirconium, hafnium, vanadium, molybdenum, and tungsten.
  • the content of ruthenium, palladium, rhodium, titanium, niobium, zirconium, hafnium, vanadium, molybdenum, tungsten (based on the metal content) in the catalytic layer is each less than 10 wt%, for example, 1 wt%, 2 wt%, 5 wt%, 8 wt%, etc., based on the total metal content of the catalytic layer.
  • the substrate may be a valve-type metal or an alloy of valve-type metals.
  • the valve-type metal may be selected from one or more of titanium, tantalum, niobium, zirconium, hafnium, vanadium, molybdenum and tungsten.
  • the substrate may be metallic titanium or titanium alloy.
  • the application also provides use of an electrode having polarity capable of being reversed, which can be used as an electrode for electrolysis, electrodialysis or electroplating.
  • the electrode may be an oxygen-evolution electrode.
  • an intermediate layer containing a platinum group metal and a platinum group metal oxide is arranged so that the firm combination between the substrate and the intermediate layer is ensured, and the corrosion resistance of the substrate when being used as a cathode is improved;
  • the prepared electrode is more tolerant towards organic solutions and can be used in a wider range of operating conditions
  • the electrode can simultaneously meet the working environment requirements of the cathode and the anode, which improves the environmental tolerance and realizes the protection of the substrate;
  • the prepared electrode has polarity capable of being reversed so as to quickly and efficiently clean deposits on the surface of the electrode
  • the oxygen-evolution electrode can still maintain an excellent electrode life when the polarity is periodically reversed, and can be applicable in fields requiring periodically reversing the polarity of the electrode.
  • FIG. 1 is a schematic diagram of current-potential relationship for Ti in acidic electrolyte
  • FIG. 2 is anodic polarization curves of Ti and its alloys in the artifificial saliva containing 0.2%NaF at a pH of 4.0;
  • FIG. 3 is anodic polarization curves of Ti-Pt alloys in the artifificial saliva containing 0.2%NaF at a pH of 4.0;
  • FIG. 4 is a schematic diagram of an electrode structure according to an example of the application.
  • a hydrogen evolution region
  • b active region
  • c active to passive transition
  • d passive region
  • Catalytic layer 3.
  • an Example of the application provides an electrode having polarity capable of being reversed, for example, as shown in FIG. 4, the electrode includes a substrate 1, an intermediate layer 2, and a catalytic layer 3, which are sequentially stacked from bottom to top.
  • the intermediate layer 2 and the catalytic layer 3 may also be symmetrically arranged on both sides of the substrate 1.
  • the substrate 1 may be a valve-type metal or an alloy of valve-type metals.
  • the valve-type metal may be selected from one of titanium, tantalum, niobium, zirconium, hafnium, vanadium, molybdenum and tungsten.
  • the substrate 1 may be metallic titanium or titanium alloy.
  • the substrate 1 may be pretreated, for example, by conventional etching or sand blasting combined with pickling.
  • the intermediate layer 2 may include a platinum group metal and a platinum group metal oxide and may be a mixture of metal platinum and iridium dioxide, and the intermediate layer 2 may also include a metal oxide of any one or more of ruthenium, palladium and rhodium.
  • the sum of the content of platinum and iridium may be 1 g/m 2 -30 g/m 2 , based on the metal content.
  • the platinum content (based on the metal content) may be 10 wt%-90 wt%, and the iridium content (based on the metal content) may be 10 wt%-90 wt%, based on the total metal content of the intermediate layer; the content of metal ruthenium, palladium and rhodium (based on the metal content) is each less than 10 wt%, based on the total metal content of the intermediate layer.
  • the platinum content (based on the metal content) may be 40 wt%-90 wt%, and the iridium content (based on the metal content) may be 10 wt%-60 wt%, based on the total metal content of the intermediate layer; the content of metal ruthenium, palladium and rhodium (based on the metal content) is each less than 10 wt%, based on the total metal content of the intermediate layer.
  • the platinum group metal used in the intermediate layer 2 has a higher oxygen-evolution potential than that of the material used in the catalytic layer 3, thus ensuring that the substrate of the electrode is not passivated under the oxygen-evolution condition.
  • the intermediate layer 2 has stable performance under hydrogen-evolution conditions and high tolerance to the working environment of the cathode. Therefore, the intermediate layer 2 can simultaneously meet the protection of the substrate when the cathode and the anode work, so that the electrode is capable of being used when its polarity is reversed, thereby quickly and efficiently cleaning deposits on the surface of the electrode and being applicable in fields requiring periodically reversing the polarity of the electrode.
  • the intermediate layer 2 is formed by coating precursor solution containing corresponding elements, drying and then sintering.
  • the precursor of platinum exists in the metal state in the subsequent sintering process, which makes the diffusion of metal platinum to the substrate 1 (e.g., titanium) easier.
  • the coating of pure metal platinum has poor stability in a highly acidic environment. Adding a certain amount of iridium (converted into iridium dioxide during sintering) can improve the stability of the intermediate layer in the highly acidic environment generated by oxygen evolution.
  • the precursor for preparing the intermediate layer 2 is formulated as a coating solution, for example chloroplatinic acid and chloroiridic acid can be formulated into a coating solution in hydrochloric acid solution, in which the platinum content may be 2.0 wt%-6.0 wt%, for example, 3.0 wt%, 4.0 wt%, 4.2 wt%, 4.8 wt%, 5.0 wt%, etc..
  • a certain amount of coating solution is applied to the pretreated substrate 1 by conventional coating methods, such as brushing, roller coating, spraying, etc..
  • the coated substrate 1 is dried in air or in an oven at 60 °C-90 °C, for example at 80 °C, and then sintered in an air circulation electric furnace at 400 °C-600 °C for 10-30 minutes, for example at 500 °C for 20 minutes. Multiple coating and sintering can be carried out, and once sintering is carried out after each coating. During the sintering process, chloroplatinic acid is decomposed into metal platinum and a small amount of platinum oxide, and chloroiridic acid is decomposed into iridium dioxide. The mixture of platinum and iridium dioxide can also be directly coated to the substrate 1 by other chemical vapor deposition or even physical vapor deposition methods.
  • the catalytic layer 3 may include a metal oxide of iridium, and may also include a mixed metal oxide of tantalum and iridium; for example, the catalytic layer 3 may include tantalum pentoxide and iridium dioxide.
  • the catalytic layer 3 may also include a metal oxide of any one or more of ruthenium, palladium, rhodium, titanium, niobium, zirconium, hafnium, vanadium, molybdenum, and tungsten.
  • the iridium content of the catalytic layer may be 3 g/m 2 -100 g/m 2 , based on the metal content.
  • the iridium content (based on the metal content) may be 20 wt%-90 wt%, and the tantalum content (based on the metal content) may be 10 wt%-80 wt%, based on the total metal content of the catalytic layer.
  • the content of metal ruthenium, palladium, rhodium, titanium, niobium, zirconium, hafnium, vanadium, molybdenum and tungsten is each less than 10 wt%, based on the total metal content of the intermediate layer.
  • the method for preparing the catalytic layer 3 is similar to the method for preparing the intermediate layer 2, for example, chloroiridic acid and tantalum pentachloride may be used as precursors, and the coating solution may be prepared in hydrochloric acid solution.
  • the intermediate layer 2 or the catalytic layer 3 may also contain other elements, and can be prepared by adding precursors of the corresponding elements to the corresponding coating solution, and chlorides of other elements may generally be added.
  • the substrate 1 and the intermediate layer 2 may be subjected to heat treatment so that some metal elements of the intermediate layer 2 can diffuse into the substrate 1.
  • the firm combination between the substrate 1 and the intermediate layer 2 is ensured, and the corrosion resistance of the substrate 1 when being used as a cathode is also improved.
  • the heat treatment may be to sinter the substrate 1 and the intermediate layer 2 in an air circulation electric furnace at 500 °C-600 °Cfor 3-6 hours, for example, at 530 °C for 4 hours.
  • Gr1 grade industrial pure titanium was used as a substrate, subjected to the heat treatment at 500 °C for 1 hour, then etched in 30.0 wt%sulfuric acid at 90 °C for 4 hours, washed in ultra-pure water by an ultrasonic device and dried in the air.
  • a coating solution for an intermediate layer was fomulated as a hydrochloric acid solution containing chloroiridic acid and chloroplatinic acid. Based on the metal content, the mass ratio of platinum to iridium was 8: 2, the platinum content was 4.8 wt%, and the concentration of HCl was 10.0 wt% (added as saturated hydrochloric acid) .
  • the coating solution for the intermediate layer was coated on the metal titanium substrate for 4 times by a thermal decomposition method (the total amount of platinum and iridium was 1.0 g/m 2 , based on the metal content, for each coating) , and the thermal decomposition was carried out at 500 °C for 20 minutes after each coating, to obtain the intermediate layer containing metal platinum and iridium dioxide. The total amount of platinum and iridium in the intermediate layer was 4.0 g/m 2 , based on the metal content.
  • the substrate and the intermediate layer were sintered at 530 °C for 4 hours.
  • a coating solution for a catalytic layer was fomulated as a hydrochloric acid solution containing chloroiridic acid and tantalum pentachloride. Based on the metal content, the mass ratio of iridium to tantalum was 7: 3, the iridium content was 6.0 wt%, and the concentration of hydrochloric acid was 10.0 wt%.
  • the coating solution for the catalyst layer was coated to the intermediate layer for 10 times by a thermal decomposition method (the amount of iridium was 1.0 g/m 2 , based on the metal content, for each coating) .
  • the thermal decomposition was carried out at 450 °C for 20 minutes after each coating, to obtain the catalytic layer containing mixed metal oxide of tantalum pentoxide and iridium dioxide.
  • the total amount of iridium in the catalytic layer was 10.0 g/m 2 , based on the metal content.
  • Gr1 grade industrial pure titanium was used as a substrate, subjected to the heat treatment at 500 °C for 1 hour, then etched in 30.0 wt%sulfuric acid at 90 °C for 4 hours, washed in ultra-pure water by an ultrasonic device and dried in the air.
  • a coating solution for an intermediate layer was fomulated as a hydrochloric acid solution containing tantalum chloride. Based on the metal content, the tantalum content was 6.0 wt%and the concentration of hydrochloric acid was 10.0 wt%.
  • the coating solution for the intermediate layer was coated on the metal titanium substrate for 3 times by a thermal decomposition method (the total amount of tantalum was 1.0 g/m 2 , based on the metal content, for each coating) , and the thermal decomposition was carried out at 520 °C for 20 minutes after each coating, to obtain the intermediate layer containing tantalum pentoxide.
  • the tantalum content in the intermediate layer was 3.0 g/m 2 , based on the metal content.
  • a coating solution for a catalytic layer was fomulated as a hydrochloric acid solution containing chloroiridic acid and tantalum pentachloride. Based on the metal content, the mass ratio of iridium to tantalum was 7: 3, the iridium content was 6.0 wt%, and the concentration of hydrochloric acid was 10.0 wt%.
  • the coating solution for the catalyst layer was coated to the intermediate layer for 14 times by a thermal decomposition method (the amount of iridium was 1.0 g/m 2 , based on the metal content, for each coating) .
  • the thermal decomposition was carried out at 450 °C for 20 minutes after each coating, to obtain the catalytic layer containing a mixed metal oxide of tantalum pentoxide and iridium dioxide.
  • the total amount of iridium in the catalytic layer was 14.0 g/m 2 , based on the metal content.
  • the positive polarity and negative polarity and current output of the rectifier were controlled by software, and the life test of the electrode was carried out under the following conditions.
  • test conditions were: 5000 A/m 2 , 15%sulfuric acid electrolyte, the time interval of polarity reversal was 5 min (i.e., during the test, the rectifier was subjected to the polarity reversal every 5 min) .
  • the accelerated life of the electrode of Example 1 was 6.1 Mah/m 2 ;
  • the accelerated life of the electrode of Comparative Example 1 was 0.3 Mah/m 2 .
  • test conditions were: 45000 A/m 2 , 80 °C, 25%sulfuric acid electrolyte, without polarity reversal.
  • the accelerated life of the electrode of Example 1 was 40.0 Mah/m 2 ;
  • the accelerated life of the electrode of Comparative Example 1 was 35.0 Mah/m 2 .
  • Accelerated life refers to a method for evaluating the performance of an electrode by enabling the electrode to reach the end of life faster than the actual work under more rigorous environments such as higher current, higher temperature, higher acidity, etc. than the actual work.
  • Gr1 grade industrial pure titanium was used as a substrate, subjected to the heat treatment at 500 °C for 1 hour, then etched in 30.0 wt%sulfuric acid at 90 °C for 4 hours, washed in ultra-pure water by an ultrasonic device and dried in the air.
  • a coating solution for an intermediate layer was fomulated as an n-butanol solution containing chloroiridic acid and chloroplatinic acid. Based on the metal content, the mass ratio of platinum to iridium was 7: 3, the platinum content was 4.2 wt%, the concentration of HCl was 2.0 wt% (added as saturated hydrochloric acid) , and the remaining component was n-butanol.
  • the coating solution for the intermediate layer was coated on the metal titanium substrate for 8 times by a thermal decomposition method (the total amount of platinum and iridium was 1.25 g/m 2 , based on the metal content, for each coating) , and the thermal decomposition was carried out at 500 °C for 20 minutes after each coating, to obtain the intermediate layer containing metal platinum and iridium dioxide.
  • the total amount of platinum and iridium in the intermediate layer was 10.0 g/m 2 , based on the metal content.
  • the substrate and the intermediate layer were sintered at 540 °C for 6 hours.
  • a coating solution for a catalyst layer was formulated as n-butanol solution containing chloroiridic acid and tantalum ethoxide. Based on the metal content, the mass ratio of iridium to tantalum was 7: 3, the iridium content was 5.0 wt%, the concentration of HCl was 2.0 wt%(added as saturated hydrochloric acid) , and the remaining component was n-butanol.
  • the coating solution for the catalyst layer was coated to the intermediate layer for 8 times by a thermal decomposition method (the amount of iridium was 1.0 g/m 2 , based on the metal content, for each coating) .
  • the thermal decomposition was carried out at 450 °C for 20 minutes after each coating, to obtain the catalytic layer containing a mixed metal oxide of tantalum pentoxide and iridium dioxide.
  • the total amount of iridium in the catalytic layer was 8.0 g/m 2 , based on the metal content.
  • Gr1 grade industrial pure titanium was used as a substrate, subjected to the heat treatment at 500 °C for 1 hour, then etched in 30.0 wt%sulfuric acid at 90 °C for 4 hours, washed in ultra-pure water by an ultrasonic device and dried in the air.
  • a coating solution for an intermediate layer was fomulated as n-butanol solution containing tantalum ethoxide. Based on the metal content, the tantalum content was 6.0 wt%.
  • the coating solution for the intermediate layer was coated on the metal titanium substrate for 3 times by a thermal decomposition method (the total amount of tantalum was 1.0 g/m 2 , based on the metal content, for each coating) , and the thermal decomposition was carried out at 500 °Cfor 20 minutes after each coating, to obtain the intermediate layer containing tantalum pentoxide.
  • the tantalum content in the intermediate layer was 3.0 g/m 2 , based on the metal content.
  • a coating solution for a catalyst layer was formulated as n-butanol solution containing chloroiridic acid and tantalum ethoxide. Based on the metal content, the mass ratio of iridium to tantalum was 7: 3 and the iridium content was 6.0 wt%.
  • the coating solution for the catalyst layer was coated to the intermediate layer for 18 times by a thermal decomposition method (the amount of iridium was 1.0 g/m 2 , based on the metal content, for each coating) .
  • the thermal decomposition was carried out at 480 °C for 20 minutes after each coating, to obtain the catalytic layer containing a mixed metal oxide of tantalum pentoxide and iridium dioxide.
  • the total amount of iridium in the catalytic layer was 18.0 g/m 2 , based on the metal content.
  • the positive polarity and negative polarity and current output of the rectifier were controlled by software, and the life test of the electrode was carried out under the following conditions.
  • test conditions were: 5000 A/m 2 , 15%sulfuric acid electrolyte, the time interval of polarity reversal was 5 min.
  • the accelerated life of the electrode of Example 2 was 10.8 Mah/m 2 ;
  • the accelerated life of the electrode of Comparative Example 2 was 0.2 Mah/m 2 .
  • test conditions were: 45000 A/m 2 , 80 °C, 25%sulfuric acid electrolyte, without polarity reversal.
  • the accelerated life of the electrode of Example 2 was 68 Mah/m 2 ;
  • the accelerated life of the electrode of Comparative Example 2 was 52.0 Mah/m 2 .
  • Example 2 has an improved service life under the condition of direct current, but has a greatly prolonged life under the condition of polarity reversal.
  • Gr1 grade industrial pure titanium was used as a substrate, subjected to the heat treatment at 500 °C for 1 hour, then etched in 7.5 wt%oxalic acid at 90 °C for 1 hour, cooled to 80 °Cand continued to etch for 12 hours, washed in ultra-pure water by an ultrasonic device and dried in the air.
  • a coating solution for an intermediate layer was fomulated as an n-butanol solution containing chloroiridic acid and chloroplatinic acid. Based on the metal content, the mass ratio of platinum to iridium was 5: 5, the platinum content was 3.0 wt%, the concentration of hydrochloric acid was 2.0 wt% (added as saturated hydrochloric acid) , and the remaining component was n-butanol.
  • the coating solution for the intermediate layer was coated on the metal titanium substrate for 2 times by a thermal decomposition method (the total amount of platinum and iridium was 1.0 g/m 2 , based on the metal content, for each coating) , and the thermal decomposition was carried out at 500 °C for 20 minutes after each coating, to obtain the intermediate layer containing metal platinum and iridium dioxide.
  • the total amount of platinum and iridium in the intermediate layer was 2.0 g/m 2 , based on the metal content.
  • the substrate and the intermediate layer were sintered at 520 °C for 3 hours.
  • a coating solution for a catalyst layer was formulated as an n-butanol solution containing chloroiridic acid and tantalum ethoxide. Based on the metal content, the mass ratio of iridium to tantalum was 7: 3 and the iridium content was 5.0 wt%.
  • the coating solution for the catalyst layer was coated to the intermediate layer for 8 times by a thermal decomposition method (the amount of iridium was 1.0 g/m 2 , based on the metal content, for each coating) .
  • the thermal decomposition was carried out at 450 °C for 20 minutes after each coating, to obtain the catalytic layer containing the mixed metal oxide of tantalum pentoxide and iridium dioxide.
  • the total amount of iridium in the catalytic layer was 8.0 g/m 2 , based on the metal content.
  • Gr1 grade industrial pure titanium was used as a substrate, subjected to the heat treatment at 500 °C for 1 hour, then etched in 7.5 wt%oxalic acid at 90 °C for 1 hour, cooled to 80 °Cand continued to etch for 12 hours, washed in ultra-pure water by an ultrasonic device and dried in the air.
  • a coating solution for an intermediate layer was fomulated as an n-butanol solution containing tantalum ethoxide and tetrabutyl titanate. Based on the metal content, the mass ratio of tantalum to titanium was 7: 3 and the tantalum content was 6.0 wt%.
  • the coating solution for the intermediate layer was coated on the metal titanium substrate for 4 times by a thermal decomposition method (the amount of a mixed titanium-tantalum oxide was 0.75 g/m 2 , based on the mixed oxide, for each coating) , and the thermal decomposition was carried out at 520 °Cfor 20 minutes after each coating, to obtain the intermediate layer containing the mixed titanium-tantalum oxide.
  • the content of the mixed titanium-tantalum oxide in the intermediate layer was 3.0 g/m 2 , based on the content of mixed oxide.
  • a coating solution for a catalyst layer was formulated as an n-butanol solution containing chloroiridic acid and tantalum ethoxide. Based on the metal content, the mass ratio of iridium to tantalum was 7: 3 and the iridium content was 6.0 wt%.
  • the coating solution for the catalyst layer was coated to the intermediate layer for 10 times by a thermal decomposition method (the amount of iridium was 1.0 g/m 2 , based on the metal content, for each coating) .
  • the thermal decomposition was carried out at 500 °C for 20 minutes after each coating, to obtain the catalytic layer containing the mixed metal oxide of tantalum pentoxide and iridium dioxide.
  • the total amount of iridium in the catalytic layer was 10.0 g/m 2 , based on the metal content.
  • the positive polarity and negative polarity and current output of the rectifier were controlled by software, and the life test of the electrode was carried out under the following conditions.
  • test conditions were: 5000 A/m 2 , 15%sulfuric acid electrolyte, the time interval of polarity reversal was 5 min.
  • the accelerated life of the electrode of Example 3 was 2.8 Mah/m 2 ;
  • the accelerated life of the electrode of Comparative Example 3 was 0.3 Mah/m 2 .
  • test conditions were: 45000 A/m 2 , 80 °C, 25%sulfuric acid electrolyte, without polarity reversal.
  • the accelerated life of the electrode of Example 3 was 27.0 Mah/m 2 ;
  • the accelerated life of the electrode of Comparative Example 3 was 24.8 Mah/m 2 .
  • Example 3 has an improved service life under the condition of direct current, but has a greatly prolonged life under the condition of polarity reversal.
  • Gr1 grade industrial pure titanium was used as a substrate, subjected to the heat treatment at 500 °C for 1 hour, then etched in 7.5 wt%oxalic acid at 90 °C for 1 hour, cooled to 80 °C and continued to etch for 12 hours, washed in ultra-pure water by an ultrasonic device and dried in the air.
  • a coating solution for an intermediate layer was fomulated as an n-butanol solution containing chloroiridic acid and chloroplatinic acid. Based on the metal content, the mass ratio of platinum to iridium was 6: 4, the platinum content was 4.0 wt%, the concentration of HCl was 2.0 wt% (added as saturated hydrochloric acid) , and the remaining component was n-butanol.
  • the coating solution for the intermediate layer was coated on the metal titanium substrate for 4 times by a thermal decomposition method (the total amount of platinum and iridium was 1.25 g/m 2 , based on the metal content, for each coating) , and the thermal decomposition was carried out at 500 °C for 20 minutes after each coating, to obtain the intermediate layer containing metal platinum and iridium dioxide.
  • the total amount of platinum and iridium in the intermediate layer was 5.0 g/m 2 , based on the metal content.
  • the substrate and the intermediate layer were sintered at 520 °C for 4 hours.
  • a coating solution for a catalyst layer was formulated as an n-butanol solution containing chloroiridic acid and tantalum ethoxide. Based on the metal content, the mass ratio of iridium to tantalum was 8: 2 and the iridium content was 4.5 wt%.
  • the coating solution for the catalyst layer was coated to the intermediate layer for 10 times by a thermal decomposition method (the amount of iridium was 1.0 g/m 2 , based on the metal content, for each coating) .
  • the thermal decomposition was carried out at 450 °C for 20 minutes after each coating, to obtain the catalytic layer containing the mixed metal oxide of tantalum pentoxide and iridium dioxide.
  • the total amount of iridium in the catalytic layer was 10.0 g/m 2 , based on the metal content.
  • Gr1 grade industrial pure titanium was used as a substrate, subjected to the heat treatment at 500 °C for 1 hour, then etched in 7.5 wt%oxalic acid at 90 °C for 1 hour, cooled to 80 °C and continued to etch for 12 hours, washed in ultra-pure water by an ultrasonic device and dried in the air.
  • a coating solution for an intermediate layer was fomulated as an n-butanol solution containing tantalum ethoxide and tetrabutyl titanate. Based on the metal content, the mass ratio of tantalum to titanium was 9: 1 and the tantalum content was 6.0 wt%.
  • the coating solution for the intermediate layer was coated on the metal titanium substrate for 4 times by a thermal decomposition method (the amount of a mixed titanium-tantalum oxide was 0.75 g/m 2 , based on the mixed oxide, for each coating) , and the thermal decomposition was carried out at 500 °C for 20 minutes after each coating, to obtain the intermediate layer containing the mixed titanium-tantalum oxide.
  • the content of the mixed titanium-tantalum oxide in the intermediate layer was 3.0 g/m 2 , based on the content of mixed oxide.
  • a coating solution for a catalyst layer was formulated as an n-butanol solution containing chloroiridic acid and tantalum ethoxide. Based on the metal content, the mass ratio of iridium to tantalum was 8: 2 and the iridium content was 4.5 wt%.
  • the coating solution for the catalyst layer was coated to the intermediate layer for 13 times by a thermal decomposition method (the amount of iridium was 1.0 g/m 2 , based on the metal content, for each coating) .
  • the thermal decomposition was carried out at 500 °C for 20 minutes after each coating, to obtain the catalytic layer containing the mixed metal oxide of tantalum pentoxide and iridium dioxide.
  • the total amount of iridium in the catalytic layer was 13.0 g/m 2 , based on the metal content.
  • the positive polarity and negative polarity and current output of the rectifier were controlled by software, and the life test of the electrode was carried out under the following conditions.
  • test conditions were: 5000 A/m 2 , 15%sulfuric acid electrolyte, the time interval of polarity reversal was 5 min.
  • the accelerated life of the electrode of Example 4 was 5.8 Mah/m 2 ;
  • the accelerated life of the electrode of Comparative Example 4 was 0.3 Mah/m 2 .
  • test conditions were: 45000 A/m 2 , 80 °C, 25%sulfuric acid electrolyte, without polarity reversal.
  • the accelerated life of the electrode of Example 4 was 32.0 Mah/m 2 ;
  • the accelerated life of the electrode of Comparative Example 4 was 37.8 Mah/m 2 .
  • Example 4 has a comparable service life under the condition of direct current, but has a greatly prolonged life under the condition of polarity reversal.
  • Gr1 grade industrial pure titanium was used as a substrate, subjected to the heat treatment at 500 °C for 1 hour, then etched in 7.5 wt%oxalic acid at 90 °C for 1 hour, cooled to 80 °Cand continued to etch for 12 hours, washed in ultra-pure water by an ultrasonic device and dried in the air.
  • a coating solution for an intermediate layer was fomulated as an n-butanol solution containing chloroiridic acid, chloroplatinic acid and ruthenium trichloride. Based on the metal content, the mass ratio of platinum: iridium: ruthenium was 60: 35: 5, the platinum content was 4.0 wt%, the concentration of HCl was 2.0 wt% (added as saturated hydrochloric acid) , and the remaining component was n-butanol.
  • the coating solution for the intermediate layer was coated on the metal titanium substrate for 6 times by a thermal decomposition method (the total amount of platinum and iridium was 1.25 g/m 2 , based on the metal content, for each coating) , and the thermal decomposition was carried out at 500 °C for 20 minutes after each coating, to obtain the intermediate layer containing metal platinum, ruthenium dioxide, and iridium dioxide.
  • the total amount of platinum and iridium in the intermediate layer was 7.5g/m 2 , based on the metal content.
  • the substrate and the intermediate layer were sintered at 520 °C for 4 hours.
  • a coating solution for a catalyst layer was formulated as an n-butanol solution containing chloroiridic acid and tantalum ethoxide. Based on the metal content, the mass ratio of iridium to tantalum was 8: 2 and the iridium content was 4.5 wt%.
  • the coating solution for the catalyst layer was coated to the intermediate layer for 22 times by a thermal decomposition method (the amount of iridium was 1.0 g/m 2 , based on the metal content, for each coating) .
  • the thermal decomposition was carried out at 450 °C for 20 minutes after each coating, to obtain the catalytic layer containing the mixed metal oxide of tantalum pentoxide and iridium dioxide.
  • the total amount of iridium in the catalytic layer was 22.0 g/m 2 , based on the metal content.
  • Gr1 grade industrial pure titanium was used as a substrate, subjected to the heat treatment at 500 °C for 1 hour, then etched in 7.5 wt%oxalic acid at 90 °C for 1 hour, cooled to 80 °Cand continued to etch for 12 hours, washed in ultra-pure water by an ultrasonic device and dried in the air.
  • a coating solution for an intermediate layer was fomulated as an n-butanol solution containing tantalum ethoxide and tetrabutyl titanate. Based on the metal content, the mass ratio of tantalum to titanium was 9: 1 and the tantalum content was 6.0 wt%.
  • the coating solution for the intermediate layer was coated on the metal titanium substrate for 4 times by a thermal decomposition method (the amount of a mixed titanium-tantalum oxide was 0.75 g/m 2 , based on the mixed oxide, for each coating) , and the thermal decomposition was carried out at 500 °Cfor 20 minutes after each coating, to obtain the intermediate layer containing the mixed titanium-tantalum oxide.
  • the content of the mixed titanium-tantalum oxide in the intermediate layer was 3.0 g/m 2 , based on the content of mixed oxide.
  • a coating solution for a catalyst layer was formulated as an n-butanol solution containing chloroiridic acid and tantalum ethoxide. Based on the metal content, the mass ratio of iridium to tantalum was 8: 2 and the iridium content was 4.5 wt%.
  • the coating solution for the catalyst layer was coated to the intermediate layer for 29 times by a thermal decomposition method (the amount of iridium was 1.0 g/m 2 , based on the metal content, for each coating) .
  • the thermal decomposition was carried out at 500 °C for 20 minutes after each coating, to obtain the catalytic layer containing the mixed metal oxide of tantalum pentoxide and iridium dioxide.
  • the total amount of iridium in the catalytic layer was 29.0 g/m 2 , based on the metal content.
  • the positive polarity and negative polarity and current output of the rectifier were controlled by software, and the life test of the electrode was carried out under the following conditions.
  • test conditions were: 5000 A/m 2 , 15%sulfuric acid electrolyte, the time interval of polarity reversal was 5 min.
  • the accelerated life of the electrode of Example 5 was 9.74 Mah/m 2 ;
  • the accelerated life of the electrode of Comparative Example 5 was 0.3 Mah/m 2 .
  • test conditions were: 45000 A/m 2 , 80 °C, 25%sulfuric acid electrolyte, without polarity reversal.
  • the accelerated life of the electrode of Example 5 was 74.0 Mah/m 2 ;
  • the accelerated life of the electrode of Comparative Example 5 was 57.8 Mah/m 2 .
  • Example 5 has an improved service life under the condition of direct current, but has a greatly prolonged life under the condition of polarity reversal.

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Abstract

La demande divulgue une électrode présentant une polarité apte à être inversée et son utilisation. L'électrode comprend un substrat comprenant un métal ou un alliage de ce dernier ; une couche intermédiaire disposée sur le substrat et comprenant un métal du groupe du platine et un oxyde métallique du groupe du platine ; et une couche catalytique disposée sur la couche intermédiaire et comprenant un oxyde métallique mixte. L'électrode peut servir d'électrode pour l'électrolyse, l'électrodialyse ou l'électrodéposition. L'électrode peut simultanément satisfaire aux exigences de conditions de travail de la cathode et de l'anode, ce qui améliore la tolérance au milieu et assure la protection du substrat ; et peut réaliser une inversion de polarité pour débarrasser rapidement et efficacement la surface de l'électrode de ses dépôts.
PCT/CN2021/076713 2020-02-17 2021-02-18 Électrode à polarité pouvant être inversée et son utilisation Ceased WO2021164702A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115874169A (zh) * 2022-12-28 2023-03-31 西安爱尔迪环保科技有限公司 长寿命极性倒换的电极制备方法
CN116219470A (zh) * 2023-03-28 2023-06-06 广东卡沃罗氢科技有限公司 具有双层阳极涂层的膜电极及其制备方法
WO2024184552A1 (fr) * 2023-03-09 2024-09-12 Magneto Special Anodes B.V. Revêtements d'oxydes métalliques mélangés appliqués à l'aide d'un dépôt spatial de couches atomiques et leurs utilisations

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113948724B (zh) * 2021-10-15 2023-11-24 上海冉昇新材料科技有限公司 一种再生式燃料电池用导电扩散层材料及其制备方法
CN115466985A (zh) * 2022-09-23 2022-12-13 中国船舶重工集团公司第七二五研究所 一种含非晶氧化铑中间层金属氧化物电极制备方法
CN118480807B (zh) * 2024-05-09 2025-11-21 洛阳船舶材料研究所(中国船舶集团有限公司第七二五研究所) 一种渗钽梯度中间层钛基金属氧化物电极及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4797182A (en) * 1986-04-17 1989-01-10 Eltech Systems Corporation Electrode with a platinum metal catalyst in surface film and its use
EP0560338A2 (fr) * 1992-03-11 1993-09-15 TDK Corporation Electrode pour dégagement d'oxygène
JP2004323955A (ja) * 2003-04-28 2004-11-18 Wako Sangyo:Kk 電解用電極及びその製造方法
JP2017115188A (ja) * 2015-12-22 2017-06-29 石福金属興業株式会社 塩素発生用電極

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4157943A (en) * 1978-07-14 1979-06-12 The International Nickel Company, Inc. Composite electrode for electrolytic processes
JPS6022075B2 (ja) * 1983-01-31 1985-05-30 ペルメレック電極株式会社 耐久性を有する電解用電極及びその製造方法
JPH0660427B2 (ja) * 1988-05-31 1994-08-10 ティーディーケイ株式会社 酸素発生用電極及びその製造方法
JP2596821B2 (ja) * 1988-12-29 1997-04-02 ダイソー株式会社 酸素発生用陽極
JP2505560B2 (ja) * 1989-01-19 1996-06-12 石福金属興業株式会社 電解用電極
JP2505563B2 (ja) * 1989-01-30 1996-06-12 石福金属興業株式会社 電解用電極
JP3212327B2 (ja) * 1991-08-30 2001-09-25 ペルメレック電極株式会社 電解用電極
JP3780410B2 (ja) * 2001-12-11 2006-05-31 大機エンジニアリング株式会社 金属メッキ用電極
JP4554542B2 (ja) * 2006-03-09 2010-09-29 石福金属興業株式会社 電解用電極
JP2008050675A (ja) * 2006-08-28 2008-03-06 Ishifuku Metal Ind Co Ltd 電解用電極
JP4884333B2 (ja) * 2007-08-24 2012-02-29 石福金属興業株式会社 電解用電極
TWI433964B (zh) * 2010-10-08 2014-04-11 Water Star Inc 複數層之混合金屬氧化物電極及其製法
JP5456744B2 (ja) * 2010-11-04 2014-04-02 ペルメレック電極株式会社 金属電解採取方法
ITMI20122030A1 (it) * 2012-11-29 2014-05-30 Industrie De Nora Spa Catodo per evoluzione elettrolitica di idrogeno
EP3296431A1 (fr) * 2016-09-15 2018-03-21 Ecole Polytechnique Fédérale de Lausanne (EPFL) Procédé de synthèse d'un électrode à utiliser comme catalyseur de la réaction d'évolution d'oxygène
JP7097042B2 (ja) * 2017-12-27 2022-07-07 石福金属興業株式会社 塩素発生用電極
US11668017B2 (en) * 2018-07-30 2023-06-06 Water Star, Inc. Current reversal tolerant multilayer material, method of making the same, use as an electrode, and use in electrochemical processes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4797182A (en) * 1986-04-17 1989-01-10 Eltech Systems Corporation Electrode with a platinum metal catalyst in surface film and its use
EP0560338A2 (fr) * 1992-03-11 1993-09-15 TDK Corporation Electrode pour dégagement d'oxygène
JP2004323955A (ja) * 2003-04-28 2004-11-18 Wako Sangyo:Kk 電解用電極及びその製造方法
JP2017115188A (ja) * 2015-12-22 2017-06-29 石福金属興業株式会社 塩素発生用電極

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BIOMATERIALS, vol. 26, 2005, pages 2239 - 2246
JAMES J. NOEL: "Doctor thesis", 1999, UNIVERSITY OF MANITOBA, article "The electrochemistry of Titanium corrosion"

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115874169A (zh) * 2022-12-28 2023-03-31 西安爱尔迪环保科技有限公司 长寿命极性倒换的电极制备方法
WO2024184552A1 (fr) * 2023-03-09 2024-09-12 Magneto Special Anodes B.V. Revêtements d'oxydes métalliques mélangés appliqués à l'aide d'un dépôt spatial de couches atomiques et leurs utilisations
CN116219470A (zh) * 2023-03-28 2023-06-06 广东卡沃罗氢科技有限公司 具有双层阳极涂层的膜电极及其制备方法
CN116219470B (zh) * 2023-03-28 2024-04-02 广东卡沃罗氢科技有限公司 具有双层阳极涂层的膜电极及其制备方法

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EP4107310A1 (fr) 2022-12-28
US20230107452A1 (en) 2023-04-06
KR20220142468A (ko) 2022-10-21
CN113337845B (zh) 2024-02-09
JP2023514281A (ja) 2023-04-05
CN113337845A (zh) 2021-09-03

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